Oxidising composition for treating keratinous materials based on amphiphilic polymers of at least an ethylenically unsaturated monomer containing a sulfonic group and comprising a hydrophobic part

ABSTRACT

The invention concerns a cosmetic composition for treating keratinous materials comprising in a carrier suitable for keratinous materials: (a) at least an amphiphilic polymer comprising at least an ethylenically unsaturated monomer with sulphonic group, in free form or partly or completely neutralised and further at least a hydrophobic part; (b) at least an oxidising agent.

[0001] The present invention relates to a gelled oxidizing compositionfor treating keratin materials, comprising an amphiphilic polymercomprising at least one ethylenically unsaturated monomer containing asulfonic group, in free form or partially or totally neutralized form,and also at least one hydrophobic portion, and also to its uses fordyeing, permanently reshaping or bleaching human keratin fibers and inparticular the hair.

[0002] It is known practice to bleach keratin fibers, and in particularhuman hair, with bleaching compositions containing one or more oxidizingagents. Among the oxidizing agents conventionally used that may bementioned are hydrogen peroxide or compounds capable of producinghydrogen peroxide by hydrolysis, such as urea peroxide or persalts, forinstance perborates, percarbonates and persulfates, hydrogen peroxideand persulfates being particularly preferred.

[0003] Said bleaching compositions are mainly in the form of anhydrousproducts (powders or creams) containing alkaline compounds (amines andalkaline silicates) and a peroxygenated reagent such as alkali metal orammonium persulfates, perborates or percarbonates, which is diluted atthe time of use with an aqueous hydrogen peroxide composition.

[0004] Bleaching compositions may also result from the mixing, at thetime of use, of the anhydrous powder of peroxygenated reagent with anaqueous composition containing the alkaline compounds and anotheraqueous composition containing hydrogen peroxide.

[0005] Bleaching compositions are also in the form of ready-to-usethickened aqueous hydrogen peroxide compositions.

[0006] For the purposes of the invention, the expression “ready-to-usecomposition” means the composition intended to be applied, withoutmodification, to the keratin fibers, i.e. it may be stored withoutmodification before use or may result from the extemporaneous mixing oftwo or more compositions.

[0007] It is moreover known practice to dye keratin fibers, and inparticular human hair, with dye compositions containing oxidation dyeprecursors, in particular ortho- or para-phenylenediamines, ortho- orpara-aminophenols, and heterocyclic compounds, which are generally knownas oxidation bases. Oxidation dye precursors, or oxidation bases, arecolorless or weakly colored compounds which, when combined withoxidizing products, can produce colored compounds and dyes by a processof oxidative condensation. It is also known that the shades obtainedwith these oxidation bases may be varied by combining them with couplersor coloration modifiers, the latter being chosen especially fromaromatic meta-diamines, meta-aminophenols, meta-diphenols and certainheterocyclic compounds such as indole compounds.

[0008] The oxidizing agent present in the oxidizing composition asdefined above may be chosen from the oxidizing agents conventionallyused for the oxidation dyeing of keratin fibers, and among which mentionmay be made of hydrogen peroxide or compounds capable of producinghydrogen peroxide by hydrolysis, such as urea peroxide or persalts, forinstance perborates and persulfates. Hydrogen peroxide is particularlypreferred.

[0009] To localize the bleaching or dye product being applied to thehair so that it does not run onto the face or outside the areas that itis intended to bleach, use has been made hitherto of conventionalthickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses,certain polyurethanes and waxes, and also, in the case of aqueousbleaching compositions, of mixtures of nonionic surfactants with an HLB(Hydrophilic-Lipophilic Balance) value, which, when suitably selected,generate the gelling effect when they are diluted with water and/orsurfactants.

[0010] However, the Applicant has found that the thickening systemsmentioned above do not produce bleaching results that are sufficientlypowerful and homogeneous, and leave the hair coarse.

[0011] Moreover, it has also been found that ready-to-use bleachingcompositions containing the oxidizing agent(s) and also the thickeningsystems of the prior art do not allow a sufficiently precise applicationwithout the composition running or without reductions in viscosity overtime.

[0012] It is also known that the technique most commonly used forpermanently reshaping the hair consists, in a first stage, in openingthe —S—S-disulfide bonds of keratin (cystine) with a compositioncontaining a suitable reducing agent (reduction step) and then, afterthe hair thus treated has been rinsed, in reconstituting said disulfidebonds in a second stage by applying to the hair, which has been placedunder tension beforehand (curlers and the like), an oxidizingcomposition (oxidation step, also known as the fixing step) so asfinally to give the hair the desired shape. This technique thus makes itpossible either to make the hair wavy or to relax it or straighten itout. The new shape given to the hair by means of a chemical treatment asabove is remarkably long-lasting and especially withstands the action ofwashing with water or shampooing, unlike the conventional simpletechniques of temporary reshaping, such as hairsetting.

[0013] The reducing compositions that may be used to carry out the firststep of a permanent-waving operation generally contain sulfites,bisulfites, alkylphosphines or, preferably, thiols, as reducing agents.Among the latter, reducing agents that are conventionally used arecysteine and its various derivatives, cysteamine and its derivatives,thiolactic acid or thioglycolic acid, the salts thereof and the estersthereof, especially glyceryl thioglycolate.

[0014] As regards the oxidizing compositions required to carry out thefixing step, use is usually made, in practice, of compositions based onaqueous hydrogen peroxide solution.

[0015] Moreover, cosmetic formulations in the form of transparent gelshave been sought for many years. This type of presentation is very muchappreciated by consumers for esthetic reasons and for reasons of easeand comfort of use.

[0016] The gel form usually presents formulators with practicalconcerns: ease with which the product can be taken from its packagingwithout significant loss, limiting of the diffusion of the product tothe local area of treatment, and ability to use amounts that aresufficient to obtain the desired cosmetic effect. This objective isimportant for oxidizing formulations used in hair dyeing, and forpermanent-waving or bleaching of the hair. These formulations mustspread well and be distributed uniformly along the keratin fibers, andmust not run onto the forehead, the nape of the neck or the face, orinto the eyes.

[0017] It is generally difficult to obtain gels based on peroxide suchas hydrogen peroxide, which are stable on storage, by using conventionalwater-soluble gelling agents and/or thickeners, for example those of thecrosslinked acrylic polymer type, for instance those sold under the nameCarbopol® by the company Goodrich. Peroxides are used in cosmetics inthe form of aqueous acidic solutions for reasons of stability. In thepresence of conventional gelling agents, they usually lead tosubstantial variations in the viscosity of the gel during storage.

[0018] Gels based on hydrogen peroxide containing a gelling agent formedby reacting a quaternized hydroxyethylcellulose such as Celquat®(product sold by National Starch), an aqueous solution at 15% by weightof a noncrosslinked poly(2-acrylamido-2-methylpropanesulfonic acid)polymer such as Cosmedia HSP-1180® (product sold by Henkel) and a sodiumpolystyrene sulfonate such as Flexan 3® (product sold by NationalStarch), used in particular concentrations, are known in U.S. Pat. No. 4804 705.

[0019] The Applicant has discovered, surprisingly, that it is possibleto obtain ready-to-use bleaching compositions that do not run, and thusremain correctly localized at the point of application, and that alsomake it possible to obtain powerful and homogeneous bleaching resultswhile at the same time leaving the hair less coarse, if an effectiveamount of a particular amphiphilic polymer is introduced into thecomposition.

[0020] The Applicant has also discovered, surprisingly, a novel familyof thickeners and/or gelling agents for obtaining transparent gels basedon oxidizing agents and preferably hydrogen peroxide or an oxidizingcompound capable of releasing hydrogen peroxide, which are stable onstorage. These agents are amphiphilic polymers comprising at least oneethylenically unsaturated monomer containing a sulfonic group, in freeform or partially or totally neutralized form, and also at least onehydrophobic portion. These novel gelling agents do not affect theoxidizing properties of the hydrogen peroxide or of a compound capableof producing hydrogen peroxide by hydrolysis, which is present in thegel thus formed.

[0021] One subject of the present invention is thus a cosmetic and/ordermatological composition for treating keratin materials, comprising,in a support that is suitable for keratin materials:

[0022] (a) at least one amphiphilic polymer comprising at least oneethylenically unsaturated monomer containing a sulfonic group, in freeform or partially or totally neutralized form, and also at least onehydrophobic portion, and

[0023] (b) at least one oxidizing agent.

[0024] The invention also relates to the use of these polymers asthickeners and/or gelling agents in cosmetic and/or dermatologicalcompositions comprising at least one oxidizing agent.

[0025] According to the invention, the oxidizing agent is preferablychosen from the group consisting of hydrogen peroxide and compoundscapable of producing hydrogen peroxide by hydrolysis, or mixturesthereof.

[0026] However, other characteristics, aspects, subjects and advantagesof the invention will emerge even more clearly on reading thedescription and the examples that follow.

Amphiphilic Polymers According to the Invention

[0027] The polymers in accordance with the invention are amphiphilicpolymers comprising at least one ethylenically unsaturated monomercontaining a sulfonic group, in free form or partially or totallyneutralized form and comprising at least one hydrophobic portion.

[0028] The expression “amphiphilic polymer” means any polymer comprisingboth a hydrophilic portion and a hydrophobic portion and especially afatty chain.

[0029] The hydrophobic portion present in the polymers of the inventionpreferably contains from 6 to 50 carbon atoms, more preferably from 6 to22 carbon atoms, even more preferably from 6 to 18 carbon atoms and moreparticularly from 12 to 18 carbon atoms.

[0030] Preferably, the polymers in accordance with the invention arepartially or totally neutralized with a mineral base (sodium hydroxide,potassium hydroxide or aqueous ammonia) or an organic base such asmono-, di- or triethanolamine, an aminomethylpropanediol,N-methylglucamine, basic amino acids, for instance arginine and lysine,and mixtures of these compounds.

[0031] The amphiphilic polymers in accordance with the inventiongenerally have a number-average molecular weight ranging from 1000 to 20000 000 g/mol, preferably ranging from 20 000 to 5 000 000 and even morepreferably from 100 000 to 1 500 000 g/mol.

[0032] The amphiphilic polymers according to the invention may or maynot be crosslinked. Crosslinked amphiphilic polymers are preferablychosen.

[0033] When they are crosslinked, the crosslinking agents may be chosenfrom polyolefinically unsaturated compounds commonly used for thecrosslinking of polymers obtained by free-radical polymerization.

[0034] Mention may be made, for example, of divinylbenzene, diallylether, dipropylene glycol diallyl ether, polyglycol diallyl ethers,triethylene glycol divinyl ether, hydroquinone diallyl ether, ethyleneglycol di(meth)acrylate or tetraethylene glycol di(meth)acrylate,trimethylolpropane triacrylate, methylenebisacrylamide,methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallylmaleate, tetraallylethylenediamine, tetraallyl-oxyethane,trimethylolpropane diallyl ether, allyl (meth)acrylate, allylic ethersof alcohols of the sugar series, or other allyl or vinyl ethers ofpolyfunctional alcohols, and also allylic esters of phosphoric and/orvinylphosphonic acid derivatives, or mixtures of these compounds.

[0035] Methylenebisacrylamide, allyl methacrylate or trimethylolpropanetriacrylate (TMPTA) will be used more particularly. The degree ofcrosslinking will generally range from 0.01 mol % to 10 mol % and moreparticularly from 0.2 mol % to 2 mol % relative to the polymer.

[0036] The ethylenically unsaturated monomers containing a sulfonicgroup are chosen especially from vinylsulfonic acid, styrenesulfonicacid, (meth)acrylamido(C₁-C₂₂)alkylsulfonic acids, andN—(C₁-C₂₂)alkyl(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids, for instanceundecylacrylamidomethanesulfonic acid, and also partially or totallyneutralized forms thereof.

[0037] (Meth)acrylamido(C₁-C₂₂)alkylsulfonic acids such as, for example,acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid,acrylamidopropane-sulfonic acid, 2-acrylamido-2-methylpropanesulfonicacid, methacrylamido-2-methylpropanesulfonic acid,2-acrylamido-n-butanesulfonic acid,2-acrylamido-2,4,4-trimethylpentanesulfonic acid,2-methacrylamidododecylsulfonic acid or2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially ortotally neutralized forms thereof, will more preferably be used.

[0038] 2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and alsopartially or totally neutralized forms thereof, will more particularlybe used.

[0039] The amphiphilic polymers in accordance with the invention may bechosen especially from random amphiphilic AMPS polymers modified byreaction with a C₆-C₂₂ n-monoalkylamine or di-n-alkylamine, and such asthose described in patent application WO-A-00/31154 (forming an integralpart of the content of the description). These polymers may also containother ethylenically unsaturated hydrophilic monomers chosen, forexample, from (meth)acrylic acids, β-substituted alkyl derivativesthereof or esters thereof obtained with monoalcohols or mono- orpolyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleicanhydride, itaconic acid or maleic acid, or mixtures of these compounds.

[0040] The preferred polymers of the invention are chosen fromamphiphilic copolymers of AMPS and of at least one ethylenicallyunsaturated hydrophobic monomer comprising at least one hydrophobicportion containing from 6 to 50 carbon atoms, more preferably from 6 to22 carbon atoms, even more preferably from 6 to 18 carbon atoms and moreparticularly 12 to 18 carbon atoms.

[0041] These same copolymers may also contain one or more ethylenicallyunsaturated monomers not comprising a fatty chain, such as (meth)acrylicacids, β-substituted alkyl derivatives thereof or esters thereofobtained with monoalcohols or mono- or polyalkylene glycols,(meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid ormaleic acid, or mixtures of these compounds.

[0042] These copolymers are described especially in patent applicationEP-A-750 899, patent U.S. Pat. No. 5,089,578 and in the followingpublications from Yotaro Morishima:

[0043] “Self-assembling amphiphilic polyelectrolytes and theirnanostructures—Chinese Journal of Polymer Science Vol. 18, No. 40,(2000), 323-336”;

[0044] “Micelle formation of random copolymers of sodium2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactantmacromonomer in water as studied by fluorescence and dynamic lightscattering—Macromolecules 2000, Vol. 33, No. 10-3694-3704”;

[0045] “Solution properties of micelle networks formed by nonionicmoieties covalently bound to a polyelectrolyte: salt effects onrheological behavior—Langmuir, 2000, Vol. 16, No. 12, 5324-5332”;

[0046] “Stimuli responsive amphiphilic copolymers of sodium2-(acrylamido)-2-methylpropanesulfonate and associativemacromonomers—Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221”.

[0047] The ethylenically unsaturated hydrophobic monomers of theseparticular copolymers are preferably chosen from the acrylates oracrylamides of formula (I) below:

[0048] in which R₁ and R₃, which may be identical or different, denote ahydrogen atom or a linear or branched C₁-C₆ alkyl radical (preferablymethyl); Y denotes O or NH; R₂ denotes a hydrophobic hydrocarbon-basedradical containing at least from 6 to 50 carbon atoms, more preferablyfrom 6 to 22 carbon atoms, even more preferably from 6 to 18 carbonatoms and more particularly from 12 to 18 carbon atoms; x denotes anumber of moles of alkylene oxide and ranges from 0 to 100.

[0049] The radical R₂ is preferably chosen from linear C₆-C₁₈ alkylradicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl andn-dodecyl) and branched or cyclic C₆-C₁₈ alkyl radicals (for examplecyclododecane (C₁₂) or adamantane (C₁₀)); C₆-C₁₈ alkylperfluoro radicals(for example the group of formula —(CH₂)₂—(CF₂)₉—CF₃); the cholesterylradical (C₂₇) or a cholesterol ester residue, for instance thecholesteryl oxyhexanoate group; aromatic polycyclic groups, for instancenaphthalene or pyrene. Among these radicals, the ones that are moreparticularly preferred are linear alkyl radicals and more particularlythe n-dodecyl radical.

[0050] According to one particularly preferred form of the invention,the monomer of formula (I) comprises at least one alkylene oxide unit(x≧1) and preferably a polyoxyalkylenated chain. The polyoxyalkylenatedchain preferably consists of ethylene oxide units and/or of propyleneoxide units and even more particularly consists of ethylene oxide units.The number of oxyalkylene units generally ranges from 3 to 100, morepreferably from 3 to 50 and even more preferably from 7 to 25.

[0051] Among these polymers, mention may be made of:

[0052] crosslinked or noncrosslinked, neutralized or nonneutralizedcopolymers comprising from 15% to 60% by weight of AMPS units and from40% to 85% by weight of (C₈-C₁₆)alkyl(meth)acrylamide units or of(C₈-C₁₆)alkyl (meth)acrylate units relative to the polymer, such asthose described in patent application EP-A-750 899;

[0053] terpolymers comprising from 10 mol % to 90 mol % of acrylamideunits, from 0.1 mol % to 10 mol % of AMPS units and from 5 mol % to 80mol % of n-(C₆-C₁₈)alkylacrylamide units, such as those described inpatent U.S. Pat. No. 5,089,578.

[0054] Mention may also be made of noncrosslinked and crosslinkedcopolymers of partially or totally neutralized AMPS and of dodecylmethacrylate, and also noncrosslinked and crosslinked copolymers ofpartially or totally neutralized AMPS and of n-dodecyl-methacrylamide,such as those described in the Morishima articles mentioned above.

[0055] Mention will be made more particularly of the copolymersconsisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units offormula (II) below:

[0056] in which X⁺ is a proton, an alkali metal cation, analkaline-earth metal cation or the ammonium ion,

[0057] and of units of formula (III) below:

[0058] in which x denotes an integer ranging from 3 to 100, preferablyfrom 5 to 80 and more preferably from 7 to 25; R₁ has the same meaningas that given above in formula (I) and R₄ denotes a linear or branchedC₆-C₂₂ and more preferably C₁₀-C₂₂ alkyl.

[0059] The polymers that are particularly preferred are those for whichx=25, R₁ denotes methyl and R₄ represents n-dodecyl; they are describedin the Morishima articles mentioned above.

[0060] The polymers for which X⁺ denotes sodium or ammonium are moreparticularly preferred.

[0061] The preferred amphiphilic polymers in accordance with theinvention may be obtained according to the standard free-radicalpolymerization processes in the presence of one or more initiators suchas, for example, azobisisobutyronitrile (AlBN),azobisdimethylvaleronitrile, ABAH(2,2-azobis[2-amidinopropane]hydrochloride), organic peroxides such asdilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc.,mineral peroxide compounds such as potassium persulfate or ammoniumpersulfate, or H₂O₂ optionally in the presence of reducing agents.

[0062] The amphiphilic polymers are obtained especially by free-radicalpolymerization in tert-butanol medium in which they precipitate.

[0063] Using precipitation polymerization in tert-butanol, it ispossible to obtain a size distribution of the polymer particles that isparticularly favorable for its uses.

[0064] The size distribution of the polymer particles may be determined,for example, by laser diffraction or image analysis.

[0065] An advantageous distribution for this type of polymer, determinedby image analysis, is as follows: 60.2% less than 423 microns, 52.0%less than 212 microns, 26.6% less than 106 microns, 2.6% less than 45microns and 26.6% greater than 850 microns.

[0066] The reaction may be performed at a temperature of between 0 and150° C., preferably between 10 and 100° C., either at atmosphericpressure or under reduced pressure. It may also be performed under inertatmosphere, and preferably under nitrogen.

[0067] According to this process 2-acrylamido-2-methylpropanesulfonicacid (AMPS) or a sodium or ammonium salt thereof was especiallypolymerized with a (meth)acrylic acid ester and

[0068] a C₁₀-C₁₈ alcohol oxyethylenated with 8 mol of ethylene oxide(Genapol® C-080 from the company Hoechst/Clariant),

[0069] a C₁₁ oxo alcohol oxyethylenated with 8 mol of ethylene oxide(Genapol® UD-080 from the company Hoechst/Clariant),

[0070] a C₁₁ oxo alcohol oxyethylenated with 7 mol of ethylene oxide(Genapol® UD-070 from the company Hoechst/Clariant),

[0071] a C₁₂-C₁₄ alcohol oxyethylenated with 7 mol of ethylene oxide(Genapol® LA-070 from the company Hoechst/Clariant),

[0072] a C₁₂-C₁₄ alcohol oxyethylenated with 9 mol of ethylene oxide(Genapol® LA-090 from the company Hoechst/Clariant),

[0073] a C₁₂-C₁₄ alcohol oxyethylenated with 11 mol of ethylene oxide(Genapol® LA-110 from the company Hoechst/Clariant),

[0074] a C₁₆-C₁₈ alcohol oxyethylenated with 8 mol of ethylene oxide(Genapol® T-080 from the company Hoechst/Clariant),

[0075] a C₁₆-C₁₈ alcohol oxyethylenated with 15 mol of ethylene oxide(Genapol® T-150 from the company Hoechst/Clariant),

[0076] a C₁₆-C₁₈ alcohol oxyethylenated with 11 mol of ethylene oxide(Genapol® T-110 from the company Hoechst/Clariant),

[0077] a C₁₆-C₁₈ alcohol oxyethylenated with 20 mol of ethylene oxide(Genapol® T-200 from the company Hoechst/Clariant),

[0078] a C₁₆-C₁₈ alcohol oxyethylenated with 25 mol of ethylene oxide(Genapol® T-250 from the company Hoechst/Clariant),

[0079] a C₁₈-C₂₂ alcohol oxyethylenated with 25 mol of ethylene oxideand/or a C₁₆-C₁₈ iso alcohol oxyethylenated with 25 mol of ethyleneoxide.

[0080] The molar % concentration of the units of formula (II) and of theunits of formula (III) in the polymers according to the invention willvary as a function of the desired cosmetic use and of the desiredrheological properties of the formulation. It may range between 0.1 mol% and 99.9 mol %.

[0081] Preferably, for the most hydrophobic polymers, the molarproportion of units of formula (I) or (Ill) ranges from 50.1% to 99.9%,more particularly from 70% to 95% and even more particularly from 80% to90%.

[0082] Preferably, for the sparingly hydrophobic polymers, the molarproportion of units of formula (I) or (III) ranges from 0.1% to 50%,more particularly from 5% to 25% and even more particularly from 10% to20%.

[0083] The monomer distribution in the polymers of the invention may be,for example, alternating, block (including multiblock) or random.

[0084] According to the invention, it is preferable for the polymers tocontain heat-sensitive pendant chains and for the aqueous solutionthereof to have a viscosity that, beyond a certain thresholdtemperature, increases or remains virtually constant as the temperatureincreases.

[0085] Even more particularly, the preferred polymers are those whoseaqueous solution has a viscosity that is low below a first thresholdtemperature and that, above this first threshold temperature, increasesto a maximum as the temperature increases, and that, above a secondthreshold temperature, decreases again as the temperature increases.From this perspective, it is preferable for the viscosity of the polymersolutions below the first threshold temperature to be from 5% to 50%, inparticular from 10% to 30% of the maximum viscosity at the secondthreshold temperature.

[0086] These polymers preferably lead in water to a phenomenon ofdemixing by heating, reflected by curves showing, as a function of thetemperature and the concentration, a minimum known as the LCST (LowerCritical Solution Temperature).

[0087] The viscosities (measured at 25° C. using a Brookfieldviscometer, needle No. 7) of the aqueous 1% solutions preferably rangefrom 20 000 mPa.s to 100 000 mPa.s and more particularly from 60 000mPa.s to 70 000 mPa.s.

[0088] The amphiphilic polymers in accordance with the invention arepresent in the compositions in concentrations ranging from 0.01% to 30%by weight of active material, more preferably from 0.1% to 10% of activematerial, even more preferably from 0.1% to 5% by weight of activematerial and even more particularly from 0.5% to 2% by weight.

Oxidizing Agent

[0089] The oxidizing agent for the composition according to theinvention is preferably chosen from the group formed by aqueous hydrogenperoxide solution, urea peroxide and persalts such as perborates orpersulfates, or mixtures thereof.

[0090] The oxidizing agent is preferably hydrogen peroxide, and evenmore preferably the oxidizing agent is aqueous hydrogen peroxidesolution.

[0091] The hydrogen peroxide concentration can range from 0.5 to 40volumes and preferably from 2 to 30 volumes, and that of the compoundcapable of forming hydrogen peroxide by hydrolysis can range from 0.1%to 25% by weight relative to the total weight of the oxidizingcomposition.

[0092] The oxidizing compositions according to the invention may beanhydrous or aqueous.

[0093] The oxidizing compositions according to the invention arepreferably aqueous and the pH of the whole aqueous oxidizing compositionpreferably ranges from 1 to 13 and even more preferably from 2 to 12.

[0094] The oxidizing composition may also be, in particular in the caseof bleaching, in the form of two parts to be mixed together at the timeof use, one of these two parts containing alkaline agents and being insolid or liquid form. For hydrogen peroxide, the pH is preferably lessthan 7 before mixing.

[0095] The pH of the aqueous oxidizing compositions according to theinvention may be obtained and/or adjusted conventionally by addingeither basifying agents, for instance aqueous ammonia, monoethanolamine,diethanolamine, triethanolamine, isopropanolamine, 1,3-propanediamine,an alkali metal or ammonium carbonate or bicarbonate, an organiccarbonate such as guanidine carbonate, or an alkali metal hydroxide, allthese compounds obviously possibly being taken alone or as a mixture, oracidifying agents, for instance hydrochloric acid, acetic acid, lacticacid or boric acid.

[0096] The oxidizing composition may contain additives that are knownfor their use in oxidizing compositions for dyeing the hair byoxidation, or for permanently reshaping or bleaching the hair, such asacidifying or basifying agents, preserving agents, sequestering agentssuch as EDTA and etidronic acid, UV-screening agents, waxes, volatile ornonvolatile, cyclic or linear or branched silicones, which areorganomodified (especially with amine groups) or not organomodified,ceramides, pseudoceramides, plant, mineral or synthetic oils, vitaminsor provitamins, for instance panthenol, opacifiers, etc.

[0097] Preferably, when the oxidizing agent is aqueous hydrogen peroxidesolution, the oxidizing composition according to the invention containsat least one stabilizer for the aqueous hydrogen peroxide solution. Incompositions combining aqueous hydrogen peroxide solution and theamphiphilic polymers of the present invention, particularly advantageousresults have been obtained by using at least one stabilizer chosen fromalkali metal or alkaline-earth metal pyrophosphates, alkali metal oralkaline-earth metal stannates, phenacetin or salts of acids and ofoxyquinoline, for instance oxyquinoline sulfate. Even moreadvantageously, at least one stannate optionally in combination with atleast one pyrophosphate is used.

[0098] Salicylic acid and its salts, pyridinedicarboxylic acid and itssalts, paracetamol and systems consisting of a) a buffer [an alkalimetal (Na or K) or ammonium borate and preferably sodium tetraboratedecahydrate], b) an alkaline agent (NH₄OH, monoethanolamine, ammoniumcarbonate, ammonium hydrogen carbonate or sodium hydroxide) and c) asequestering agent for a heavy metal ion (Fe, Mn or Cu), such as thosedescribed in patent applications WO-01/72271, WO-01/72272 andWO-01/52801, may also be used.

[0099] In the oxidizing compositions according to the invention, theconcentration of stabilizers for the aqueous hydrogen peroxide solutioncan range from 0.0001% to 5% by weight and preferably from 0.01% to 2%by weight relative to the total weight of the oxidizing compositions.

[0100] In the oxidizing compositions according to the inventioncontaining aqueous hydrogen peroxide solution, the ratio of theconcentrations of the hydrogen peroxide to the stabilizers can rangefrom 0.05 to 1000, preferably from 0.1 to 500 and even more preferablyfrom 1 to 200. Similarly, the ratio of the concentrations of theamphiphilic polymer(s) according to the invention to the stabilizers canrange from 0.05 to 1000, preferably from 0.1 to 500 and even morepreferably from 1 to 200.

[0101] In the oxidizing compositions according to the invention, theconcentration of oxidizing agents ranges from 0.1% to 25% by weightrelative to the total weight of the composition.

[0102] Preferably, according to the invention, the ratio of theconcentrations of the amphiphilic polymer(s) according to the inventionto the oxidizing agents is between 0.001 and 10, the amounts of saidpolymers and oxidizing agents being expressed as active materials(hydrogen peroxide for the aqueous hydrogen peroxide solution). Evenmore preferably, this ratio is between 0.01 and 5 and even moreparticularly between 0.02 and 1.

[0103] When the compositions according to the invention are generally inthe form of a transparent gel, their viscosity preferably ranges from 50mPa.s to 10 Pa.s and more preferably from 75 mPa.s to 0.5 Pa.s.

[0104] More particularly, the compositions according to the inventionmay also comprise at least one amphoteric or cationic substantivepolymer.

Cationic Polymers

[0105] For the purposes of the present invention, the expression“cationic polymer” denotes any polymer containing cationic groups and/orgroups which may be ionized into cationic groups.

[0106] The cationic polymers which may be used in accordance with thepresent invention may be chosen from any of those already known per seas improving the cosmetic properties of the hair, namely, in particular,those described in patent application EP-A-337 354 and in French patentsFR-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.

[0107] The cationic polymers that are preferred are chosen from thosecontaining units comprising primary, secondary, tertiary and/orquaternary amine groups, which may either form part of the main polymerchain or may be borne by a side substituent directly attached thereto.

[0108] The cationic polymers used generally have a number-averagemolecular mass of between 500 and 5×10⁶ approximately and preferablybetween 10³ and 3×10⁶ approximately.

[0109] Among the cationic polymers which may be mentioned moreparticularly are polymers of the polyamine, polyamino amide andpolyquaternary ammonium type.

[0110] These are known products. They are described in particular inFrench patents 2 505 348 and 2 542 997. Among said polymers, mention maybe made of:

[0111] (1) homopolymers or copolymers derived from acrylic ormethacrylic esters or amides and comprising at least one of the units offormula (I), (II), (III) or (IV) below:

[0112] in which:

[0113] R₃, which may be identical or different, denote a hydrogen atomor a CH₃ radical;

[0114] A, which may be identical or different, represent a linear orbranched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbonatoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;

[0115] R₄, R₅ and R₆, which may be identical or different, represent analkyl group containing from 1 to 18 carbon atoms or a benzyl radical andpreferably an alkyl group containing from 1 to 6 carbon atoms;

[0116] R₁ and R₂, which may be identical or different, representhydrogen or an alkyl group containing from 1 to 6 carbon atoms, andpreferably methyl or ethyl;

[0117] X denotes an anion derived from an inorganic or organic acid,such as a methosulfate anion or a halide such as chloride or bromide.

[0118] The polymers of family (1) can also contain one or more unitsderived from comonomers which may be chosen from the family ofacrylamides, methacrylamides, diacetoneacrylamides, acrylamides andmethacrylamides substituted on the nitrogen with lower (C₁-C₄) alkyls,acrylic or methacrylic acids or esters thereof, vinyllactams such asvinylpyrrolidone or vinylcaprolactam, and vinyl esters.

[0119] Thus, among these polymers of family (1), mention may be made of:

[0120] copolymers of acrylamide and of dimethylaminoethyl methacrylatequaternized with dimethyl sulfate or with a dimethyl halide, such as theproduct sold under the name Hercofloc by the company Hercules,

[0121] the copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium chloride described, for example,in patent application EP-A-080 976 and sold under the name Bina Quat P100 by the company Ciba Geigy,

[0122] the copolymer of acrylamide and ofmethacryloyloxyethyltrimethylammonium methosulfate sold under the nameReten by the company Hercules,

[0123] quaternized or nonquaternized vinylpyrrolidone/dialkylaminoalkylacrylate or methacrylate copolymers, such as the products sold under thename “Gafquat” by the company ISP, such as, for example, “Gafquat 734”or “Gafquat 755”, or alternatively the products known as “Copolymer 845,958 and 937”. These polymers are described in detail in French patents 2077 143 and 2 393 573,

[0124] dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidoneterpolymers, such as the product sold under the name Gaffix VC 713 bythe company ISP,

[0125] vinylpyrrolidone/methacrylamidopropyldimethylamine copolymerssold in particular under the name Styleze CC 10 by ISP, and

[0126] quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamidecopolymers such as the product sold under the name “Gafquat HS 100” bythe company ISP.

[0127] (2) The cellulose ether derivatives containing quaternaryammonium groups, described in French patent 1 492 597, and in particularthe polymers sold under the names “JR” (JR 400, JR 125 and JR 30M) or“LR” (LR 400, or LR 30M) by the company Union Carbide Corporation. Thesepolymers are also defined in the CTFA dictionary as quaternary ammoniumsof hydroxyethylcellulose that has reacted with an epoxide substitutedwith a trimethylammonium group.

[0128] (3) Cationic cellulose derivatives such as cellulose copolymersor cellulose derivatives grafted with a water-soluble monomer ofquaternary ammonium, and described in particular in U.S. Pat. No.4,131,576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-,hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with amethacryloyloxyethyltrimethylammonium,methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

[0129] The commercial products corresponding to this definition are moreparticularly the products sold under the names “Celquat L 200” and“Celquat H 100” by the company National Starch.

[0130] (4) The cationic polysaccharides described more particularly inU.S. Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containingcationic trialkylammonium groups. Guar gums modified with a salt (e.g.chloride) of 2,3-epoxypropyltrimethylammonium are used, for example.

[0131] Such products are sold in particular under the trade names JaguarC13 S, Jaguar C 15, Jaguar C 17 or Jaguar C162 by the company Meyhall.

[0132] (5) Polymers consisting of piperazinyl units and of divalentalkylene or hydroxyalkylene radicals containing straight or branchedchains, optionally interrupted by oxygen, sulfur or nitrogen atoms or byaromatic or heterocyclic rings, and also the oxidation and/orquaternization products of these polymers. Such polymers are described,in particular, in French patents 2 162 025 and 2 280 361.

[0133] (6) Water-soluble polyamino amides prepared in particular bypolycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, adianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, abis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkylhalide or alternatively with an oligomer resulting from the reaction ofa difunctional compound which is reactive with a bis-halohydrin, abis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, anepihalohydrin, a diepoxide or a bis-unsaturated derivative; thecrosslinking agent being used in proportions ranging from 0.025 to 0.35mol per amine group of the polyamino amide; these polyamino amides canbe alkylated or, if they contain one or more tertiary amine functions,they can be quaternized. Such polymers are described, in particular, inFrench patents 2 252 840 and 2 368 508.

[0134] (7) The polyamino amide derivatives resulting from thecondensation of polyalkylene polyamines with polycarboxylic acidsfollowed by alkylation with difunctional agents. Mention may be made,for example, of adipic acid/dialkylaminohydroxyalkyldialkylene-triaminepolymers in which the alkyl radical contains from 1 to 4 carbon atomsand preferably denotes methyl, ethyl or propyl. Such polymers aredescribed in particular in French patent 1 583 363.

[0135] Among these derivatives, mention may be made more particularly ofthe adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymerssold under the name “Cartaretine F, F4 or F8” by the company Sandoz.

[0136] (8) The polymers obtained by reaction of a polyalkylene polyaminecontaining two primary amine groups and at least one secondary aminegroup with a dicarboxylic acid chosen from diglycolic acid and saturatedaliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molarratio between the polyalkylene polyamine and the dicarboxylic acid isbetween 0.8:1 and 1.4:1; the polyamino amide resulting therefrom isreacted with epichlorohydrin in a molar ratio of epichlorohydrinrelative to the secondary amine group of the polyamino amide of between0.5:1 and 1.8:1. Such polymers are described in particular in U.S. Pat.Nos. 3,227,615 and 2,961,347.

[0137] Polymers of this type are sold in particular under the name“Hercosett 57” by the company Hercules Inc. or alternatively under thename “PD 170” or “Delsette 101” by the company Hercules in the case ofthe adipic acid/epoxypropyl/diethylenetriamine copolymer.

[0138] (9) Cyclopolymers of alkyldiallylamine or ofdialkyldiallylammonium, such as the homopolymers or copolymerscontaining, as main constituent of the chain, units corresponding toformula (V) or (VI):

[0139] in which formulae k and t are equal to 0 or 1, the sum k+t beingequal to 1; R₉ denotes a hydrogen atom or a methyl radical; R₇ and R₈,independently of each other, denote an alkyl group having from 1 to 8carbon atoms, a hydroxyalkyl group in which the alkyl group preferablyhas 1 to 5 carbon atoms, a lower C₁-C₄ amidoalkyl group, or R₇ and R₈can denote, together with the nitrogen atom to which they are attached,heterocyclic groups such as piperidyl or morpholinyl; R₇ and R₈,independently of each other, preferably denote an alkyl group havingfrom 1 to 4 carbon atoms; Y is an anion such as bromide, chloride,acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate orphosphate. These polymers are described in particular in French patent 2080 759 and in its Certificate of Addition 2 190 406.

[0140] Among the polymers defined above, mention may be made moreparticularly of the dimethyldiallylammonium chloride homopolymer soldunder the name “Merquat 100” by the company Calgon (and its homologs oflow weight-average molecular mass) and copolymers ofdiallyidimethylammonium chloride and of acrylamide, sold under the name“Merquat 550”.

[0141] (10) The quaternary diammonium polymer containing repeating unitscorresponding to the formula:

[0142] in which formula (VII):

[0143] R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different,represent aliphatic, alicyclic or arylaliphatic radicals containing from1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, oralternatively R₁₀, R₁₁, R₁₂ and R₁₃, together or separately, constitute,with the nitrogen atoms to which they are attached, heterocyclesoptionally containing a second hetero atom other than nitrogen, oralternatively R₁₀, R₁₁, R₁₂ and R₁₃ represent a linear or branched C₁-C₆alkyl radical substituted with a nitrile, ester, acyl or amide group ora group —CO—O—R₁₄-D or —CO—NH—R₁₄-D where R₁₄ is an alkylene and D is aquaternary ammonium group;

[0144] A₁ and B₁ represent polymethylene groups containing from 2 to 20carbon atoms which may be linear or branched, saturated or unsaturated,and which may contain, linked to or intercalated in the main chain, oneor more aromatic rings or one or more oxygen or sulfur atoms orsulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternaryammonium, ureido, amide or ester groups, and

[0145] X⁻ denotes an anion derived from a mineral or organic acid;

[0146] A₁, R₁₀ and R₁₂ can form, with the two nitrogen atoms to whichthey are attached, a piperazine ring; in addition, if A₁ denotes alinear or branched, saturated or unsaturated alkylene or hydroxyalkyleneradical, B₁ can also denote a group —(CH₂)_(n)—CO-D-OC—(CH₂)_(n)— inwhich D denotes:

[0147] a) a glycol residue of formula: —O-Z-O—, where Z denotes a linearor branched hydrocarbon-based radical or a group corresponding to one ofthe following formulae:

—(CH₂—CH₂—O)_(x)—CH₂—CH₂—

—[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—

[0148]  where x and y denote an integer from 1 to 4, representing adefined and unique degree of polymerization or any number from 1 to 4representing an average degree of polymerization;

[0149]  b) a bis-secondary diamine residue such as a piperazinederivative;

[0150]  c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Ydenotes a linear or branched hydrocarbon-based radical, or alternativelythe divalent radical

—CH₂—CH₂—S—S—CH₂—CH₂—;

[0151]  d) a ureylene group of formula: —NH—CO—NH—.

[0152] Preferably, X⁻ is an anion such as chloride or bromide.

[0153] These polymers generally have a number-average molecular mass ofbetween 1000 and 100 000.

[0154] Polymers of this type are described in particular in Frenchpatents 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 andU.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462,2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904,4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

[0155] It is more particularly possible to use polymers that consist ofrepeating units corresponding to formula (VIII) below:

[0156] in which R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical ordifferent, denote an alkyl or hydroxyalkyl radical containing from 1 to4 carbon atoms approximately, n and p are integers ranging from 2 to 20approximately, and X⁻ is an anion derived from a mineral or organicacid.

[0157] (11) Polyquaternary ammoniums consisting of repeating units offormula (IX):

[0158] in which p denotes an integer ranging from 1 to 6 approximately,D may be nothing or may represent a group —(CH₂)_(r)—CO— in which rdenotes a number equal to 4 or to 7, X⁻ is an anion.

[0159] Such polymers may be prepared according to the processesdescribed in U.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They aredescribed in particular in patent application EP-A-122 324.

[0160] Among these products, mention may be made, for example, of“Mirapol A 15”, “Mirapol AD1”, “Mirapol AZ1” and “Mirapol 175” sold bythe company Miranol.

[0161] (12) Quaternary polymers of vinylpyrrolidone and ofvinylimidazole, such as, for example, the products sold under the namesLuviquat FC 905, FC 550 and FC 370 by the company BASF.

[0162] (13) Polyamines such as Polyquart H sold by Henkel, which aregiven under the reference name “Polyethylene glycol (15) tallowpolyamine” in the CTFA dictionary.

[0163] (14) Crosslinkedmethacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkylammonium salt polymers such asthe polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization ofacrylamide with dimethylaminoethyl methacrylate quaternized with methylchloride, the homo- or copolymerization being followed by crosslinkingwith an olefinically unsaturated compound, in particularmethylenebisacrylamide. A crosslinkedacrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer(20/80 by weight) in the form of a dispersion containing 50% by weightof said copolymer in mineral oil can be used more particularly. Thisdispersion is sold under the name “Salcare® SC 92” by the company AlliedColloids. A crosslinked methacryloyloxyethyltrimethylammonium chloridehomopolymer containing about 50% by weight of the homopolymer in mineraloil or in a liquid ester can also be used. These dispersions are soldunder the names “Salcare® SC 95” and “Salcare® SC 96” by the companyAllied Colloids.

[0164] Other cationic polymers which can be used in the context of theinvention are polyalkyleneimines, in particular polyethyleneimines,polymers containing vinylpyridine or vinylpyridinium units, condensatesof polyamines and of epichlorohydrin, quaternary polyureylenes andchitin derivatives.

[0165] Among all the cationic polymers which may be used in the contextof the present invention, it is preferred to use the polymers offamilies (1), (9), (10), (11) and (14) and even more preferably thepolymers consisting of repeating units of formulae (W) and (U) below:

[0166] and in particular those whose weight-average molar mass,determined by gel permeation chromatography, is between 9500 and 9900;

[0167] and in particular those whose weight-average molar mass,determined by gel permeation chromatography, is about 1200.

[0168] The concentration of cationic polymer in the compositionaccording to the present invention may range from 0.01% to 10% by weightrelative to the total weight of the composition, preferably from 0.05%to 5% and even more preferably from 0.1% to 3%.

Amphoteric Polymers

[0169] The amphoteric polymers which may be used in accordance with thepresent invention may be chosen from polymers comprising units K and Mrandomly distributed in the polymer chain, in which K denotes a unitderived from a monomer comprising at least one basic nitrogen atom and Mdenotes a unit derived from an acidic monomer comprising one or morecarboxylic or sulfonic groups, or alternatively K and M may denotegroups derived from zwitterionic carboxybetaine or sulfobetainemonomers; K and M may also denote a cationic polymer chain comprisingprimary, secondary, tertiary or quaternary amine groups, in which atleast one of the amine groups bears a carboxylic or sulfonic grouplinked via a hydrocarbon-based radical, or alternatively K and M formpart of a chain of a polymer containing an α,β-dicarboxylic ethyleneunit in which one of the carboxylic groups has been made to react with apolyamine comprising one or more primary or secondary amine groups.

[0170] The amphoteric polymers corresponding to the above definitionthat are more particularly preferred are chosen from the followingpolymers:

[0171] (1) polymers resulting from the copolymerization of a monomerderived from a vinyl compound bearing a carboxylic group such as, moreparticularly, acrylic acid, methacrylic acid, maleic acid,α-chloroacrylic acid, and a basic monomer derived from a substitutedvinyl compound containing at least one basic atom, such as, moreparticularly, dialkylaminoalkyl methacrylate and acrylate,dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds aredescribed in U.S. Pat. No. 3,836,537.

[0172] Mention may also be made of the sodiumacrylate/acrylamidopropyltrimethyl-ammonium chloride copolymer soldunder the name Polyquart KE 3033 by the company Henkel.

[0173] The vinyl compound may also be a dialkyldiallylammonium salt suchas dimethyldiallylammonium chloride. The copolymers of acrylic acid andof the latter monomer are sold under the names Merquat 280, Merquat 295and Merquat Plus 3330 by the company Calgon.

[0174] (2) polymers containing units derived from:

[0175] a) at least one monomer chosen from acrylamides andmethacrylamides substituted on the nitrogen with an alkyl radical,

[0176] b) at least one acidic comonomer containing one or more reactivecarboxylic groups, and

[0177] c) at least one basic comonomer such as esters containingprimary, secondary, tertiary and quaternary amine substituents ofacrylic and methacrylic acids and the product of quaternization ofdimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

[0178] The N-substituted acrylamides or methacrylamides which are moreparticularly preferred according to the invention are groups in whichthe alkyl radicals contain from 2 to 12 carbon atoms and moreparticularly N-ethylacrylamide, N-tert-butylacrylamide,N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide,N-dodecylacrylamide and the corresponding methacrylamides.

[0179] The acidic comonomers are chosen more particularly from acrylicacid, methacrylic acid, crotonic acid, itaconic acid, maleic acid andfumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleicor fumaric acids or anhydrides.

[0180] The preferred basic comonomers are aminoethyl, butylaminoethyl,N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

[0181] The copolymers whose CTFA (4th edition, 1991) name isoctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such asthe products sold under the name Amphomer or Lovocryl 47 by the companyNational Starch are particularly used.

[0182] (3) crosslinked and alkylated polyamino amides partially ortotally derived from polyamino amides of general formula:

[0183]

[0184] in which R₁₉ represents a divalent radical derived from asaturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acidcontaining an ethylenic double bond, an ester of a lower alkanol, having1 to 6 carbon atoms, of these acids or a radical derived from theaddition of any one of said acids to a bis(primary) or bis(secondary)amine, and Z denotes a bis(primary), mono- orbis(secondary)polyalkylene-polyamine radical and preferably represents:

[0185] a) in proportions of from 60 to 100 mol %, the radical

[0186] where x=2 and p=2 or 3, or alternatively x=3 and p=2 this radicalbeing derived from diethylenetriamine, from triethylenetetraamine orfrom dipropylenetriamine;

[0187] b) in proportions of from 0 to 40 mol %, the radical (XI) abovein which x=2 and p=1 and which is derived from ethylenediamine, or theradical derived from piperazine:

[0188] c) in proportions of from 0 to 20 mol %, the —NH—(CH₂)₆—NH—radical derived from hexamethylenediamine, these polyamino amines beingcrosslinked by addition of a difunctional crosslinking agent chosen fromepihalohydrins, diepoxides, dianhydrides and bis-unsaturatedderivatives, using from 0.025 to 0.35 mol of crosslinking agent peramine group of the polyamino amide and alkylated by the action ofacrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.

[0189] The saturated carboxylic acids are preferably chosen from acidshaving 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipicacid and 2,4,4-trimethyladipic acid, terephthalic acid and acidscontaining an ethylenic double bond such as, for example, acrylic acid,methacrylic acid and itaconic acid.

[0190] The alkane sultones used in the alkylation are preferably propanesultone or butane sultone, and the salts of the alkylating agents arepreferably the sodium or potassium salts.

[0191] (4) polymers containing zwitterionic units of formula:

[0192] in which R₂₀ denotes a polymerizable unsaturated group such as anacrylate, methacrylate, acrylamide or methacrylamide group, y and zrepresent an integer from 1 to 3, R₂₁ and R₂₂ represent a hydrogen atom,methyl, ethyl or propyl, R₂₃ and R₂₄ represent a hydrogen atom or analkyl radical such that the sum of the carbon atoms in R₂₃ and R₂₄ doesnot exceed 10.

[0193] The polymers comprising such units can also contain units derivedfrom nonzwitterionic monomers such as dimethyl or diethylaminoethylacrylate or methacrylate or alkyl acrylates or methacrylates,acrylamides or methacrylamides or vinyl acetate.

[0194] By way of example, mention may be made of the copolymer of butylmethacrylate/dimethylcarboxymethylammonioethyl methacrylate such as theproduct sold under the name Diaformer Z301 by the company Sandoz.

[0195] (5) polymers derived from chitosan, described in particular inFrench patent No. 2 137 684 or U.S. Pat. No. 3,879,376, containingmonomer units corresponding to formulae (XIII), (XIV) and (XV) below:

[0196] the unit (XIII) being present in proportions of between 0 and30%, the unit (XIV) in proportions of between 5% and 50% and the unit(XV) in proportions of between 30% and 90%, it being understood that, inthis unit (XV), R₂₅ represents a radical of formula:

[0197] in which q denotes zero or 1;

[0198] if q=0, R₂₆, R₂₇ and R₂₈, which may be identical or different,each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or aminoresidue, a monoalkylamine residue or a dialkylamine residue which areoptionally interrupted by one or more nitrogen atoms and/or optionallysubstituted with one or more amine, hydroxyl, carboxyl, alkylthio orsulfonic groups, an alkylthio residue in which the alkyl group bears anamino residue, at least one of the radicals R₂₆, R₂₇ and R₂₈ being, inthis case, a hydrogen atom;

[0199] or, if q=1, R₂₆, R₂₇ and R₂₈ each represent a hydrogen atom, andalso the salts formed by these compounds with bases or acids.

[0200] Polymers of this type that are more particularly preferredcomprise from 0 to 20% by weight of units (XIII), from 40% to 50% byweight of units (XIV) and from 40% to 50% by weight of units (XV) inwhich R₂₅ denotes the radical —CH₂—CH₂—.

[0201] (6) polymers derived from the N-carboxyalkylation of chitosan,such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under thename “Evalsan” by the company Jan Dekker.

[0202] (7) polymers corresponding to the general formula (XI) asdescribed, for example, in French patent 1 400 366:

[0203] in which R₂₉ represents a hydrogen atom, a CH₃O, CH₃CH₂O orphenyl radical, R₃₀ denotes hydrogen or a lower alkyl radical such asmethyl or ethyl, R₃₁ denotes hydrogen or a lower alkyl radical such asmethyl or ethyl, R₃₂ denotes a lower alkyl radical such as methyl orethyl or a radical corresponding to the formula: —R₃₃—N(R₃₁)₂, R₃₃representing a —CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)— group, R₃₁having the meanings mentioned above,

[0204] and also the higher homologs of these radicals and containing upto 6 carbon atoms,

[0205] r is such that the molecular weight is between 500 and 6 000 000and preferably between 1000 and 1 000 000.

[0206] (8) amphoteric polymers of the type -D-X-D-X- chosen from:

[0207] a) polymers obtained by the action of chloroacetic acid or sodiumchloroacetate on compounds containing at least one unit of formula:

-D-X-D-X-D-   (XVII)

[0208] where D denotes a radical

[0209] and X denotes the symbol E or E′, E or E′, which may be identicalor different, denote a divalent radical which is an alkylene radicalwith a straight or branched chain containing up to 7 carbon atoms in themain chain, which is unsubstituted or substituted with hydroxyl groupsand which can contain, in addition to the oxygen, nitrogen and sulfuratoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogenand sulfur atoms being present in the form of ether, thioether,sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups,hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide,alcohol, ester and/or urethane groups;

[0210] b) polymers of formula:

-D-X-D-X-   (XVIII)

[0211] where D denotes a radical

[0212] and X denotes the symbol E or E′ and at least once E′; E havingthe meaning given above and E′ being a divalent radical which is analkylene radical with a straight or branched chain having up to 7 carbonatoms in the main chain, which is unsubstituted or substituted with oneor more hydroxyl radicals and containing one or more nitrogen atoms, thenitrogen atom being substituted with an alkyl chain which is optionallyinterrupted by an oxygen atom and necessarily containing one or morecarboxyl functions or one or more hydroxyl functions and betainized byreaction with chloroacetic acid or sodium chloroacetate.

[0213] (9) (C₁-C₅)alkyl vinyl ether/maleic anhydride copolymerspartially modified by semiamidation with an N,N-dialkylaminoalkylaminesuch as N,N-dimethylaminopropyl-amine or by semiesterification with anN,N-dialkanolamine. These copolymers can also contain other vinylcomonomers such as vinylcaprolactam.

[0214] The amphoteric polymers that are particularly preferred accordingto the invention are those of family (1).

[0215] According to the invention, the amphoteric polymer(s) mayrepresent from 0.01% to 10% by weight, preferably from 0.05% to 5% byweight and even more preferably from 0.1% to 3% by weight relative tothe total weight of the composition.

[0216] The compositions of the invention preferably comprise one or moresurfactants.

[0217] The surfactants may be chosen, without discrimination, alone oras mixtures, from anionic, amphoteric, nonionic, zwitterionic andcationic surfactants.

[0218] The surfactants that are suitable for carrying out the presentinvention are especially the following:

(i) Anionic Surfactant(s)

[0219] By way of example of anionic surfactants which can be used, aloneor as mixtures, in the context of the present invention, mention may bemade in particular (nonlimiting list) of salts (in particular alkalimetal salts, especially sodium salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts) of the following compounds: alkylsulfates, alkyl ether sulfates, alkylamido ether sulfates,alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulfonates,alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates, α-olefinsulfonates, paraffin sulfonates; (C₆-C₂₄)alkyl sulfosuccinates,(C₆-C₂₄)alkyl ether sulfosuccinates, (C₆-C₂₄)alkylamide sulfosuccinates;(C₆-C₂₄)alkyl sulfoacetates; (C₆-C₂₄)acyl sarcosinates; and (C₆-C₂₄)acylglutamates. It is also possible to use (C₆-C₂₄)alkylpolyglycosidecarboxylic esters such as alkylglucoside citrates, alkylpolyglycosidetartrates and alkylpolyglycoside sulfosuccinates,alkylsulfo-succinamates; acyl isethionates and N-acyl taurates, thealkyl or acyl radical of all of these different compounds preferablycontaining from 12 to 20 carbon atoms and the aryl radical preferablydenoting a phenyl or benzyl group. Among the anionic surfactants whichcan also be used, mention may also be made of fatty acid salts such asoleic, ricinoleic, palmitic and stearic acid salts, coconut oil acid orhydrogenated coconut oil acid; acyl lactylates in which the acyl radicalcontains 8 to 20 carbon atoms. It is also possible to use alkylD-galactoside uronic acids and their salts, polyoxyalkylenated(C₆-C₂₄)alkyl ether carboxylic acids, polyoxyalkylenated(C₆-C₂₄)alkylaryl ether carboxylic acids, polyoxyalkylenated(C₆-C₂₄)alkylamido ether carboxylic acids and their salts, in particularthose containing from 2 to 50 alkylene oxide groups, in particularethylene oxide groups, and mixtures thereof.

(ii) Nonionic Surfactant(s)

[0220] The nonionic surfactants are, themselves also, compounds that arewell known per se (see in particular in this respect “Handbook ofSurfactants” by M. R. Porter, published by Blackie & Son (Glasgow andLondon), 1991, pp. 116-178) and their nature is not a critical factor inthe context of the present invention. Thus, they can be chosen inparticular from (nonlimiting list) polyethoxylated or polypropoxylated,alkylphenols, alpha-diols or alcohols, having a fatty chain containing,for example, 8 to 18 carbon atoms, it being possible for the number ofethylene oxide or propylene oxide groups to range in particular from 2to 50. Mention may also be made of copolymers of ethylene oxide and ofpropylene oxide, condensates of ethylene oxide and of propylene oxidewith fatty alcohols; polyethoxylated fatty amides preferably having from2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containingon average 1 to 5, and in particular 1.5 to 4, glycerol groups;polyethoxylated fatty amines preferably having 2 to 30 mol of ethyleneoxide; oxyethylenated fatty acid esters of sorbitan having from 2 to 30mol of ethylene oxide; fatty acid esters of sucrose, fatty acid estersof polyethylene glycol, alkylpolyglycosides, N-alkylglucaminederivatives, and amine oxides such as (C₁₀-C₁₄)alkylamine oxides orN-acylaminopropylmorpholine oxides. It will be noted thatalkylpolyglycosides are nonionic surfactants that are particularlysuitable within the context of the present invention.

(iii) Amphoteric or Zwitterionic Surfactant(s)

[0221] The amphoteric or zwitterionic surfactants, the nature of whichis not a critical factor in the context of the present invention, canbe, in particular (nonlimiting list), aliphatic secondary or tertiaryamine derivatives in which the aliphatic radical is a linear or branchedchain containing 8 to 18 carbon atoms and containing at least onewater-solubilizing anionic group (for example carboxylate, sulfonate,sulfate, phosphate or phosphonate); mention may also be made of(C₈-C₂₀)alkylbetaines, sulfobetaines,(C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines or(C₈-C₂₀)alkylamido(C₁-C₆)alkylsulfobetaines.

[0222] Among the amine derivatives, mention may be made of the productssold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982,under the names Amphocarboxyglycinates and Amphocarboxypropionates, withthe respective structures:

R₂—CONHCH₂CH₂—N(R₃)(R₄)(CH₂COO⁻)

[0223] in which: R₂ denotes an alkyl radical of an acid R₂—COOH presentin hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical, R₃denotes a beta-hydroxyethyl group and R₄ denotes a carboxymethyl group;and

R₂—CONHCH₂CH₂—N(B)(C)

[0224] in which:

[0225] B represents —CH₂CH₂OX′, C represents —(CH₂)_(z)—Y′, with z=1 or2,

[0226] X′ denotes the —CH₂CH₂—COOH group or a hydrogen atom,

[0227] Y′ denotes —COOH or the —CH₂—CHOH—SO₃H radical,

[0228] R₂′ denotes an alkyl radical of an acid R₉—COOH present incoconut oil or in hydrolyzed linseed oil, an alkyl radical, inparticular a C₇, C₉, C₁₁ or C₁₃ alkyl radical, a C₁₇ alkyl radical andits iso form, or an unsaturated C₁₇ radical.

[0229] These compounds are classified in the CTFA dictionary, 5thedition, 1993, under the names Disodium Cocoamphodiacetate, DisodiumLauroamphodiacetate, Disodium Caprylamphodiacetate, DisodiumCapryloamphodiacetate, Disodium Cocoampho-dipropionate, DisodiumLauroamphopropionate, Disodium Caprylamphodipropionate, DisodiumCaprylamphodipropionate, Lauroamphodipropionic acid andCocoampho-dipropionic acid.

[0230] By way of example, mention may be made of the cocoamphodiacetatesold under the trade name Miranol® C2M concentrate by the company RhodiaChimie.

(iv) Cationic Surfactants

[0231] Among the cationic surfactants, mention may be made in particular(nonlimiting list) of: salts of optionally polyoxyalkylenated primary,secondary or tertiary fatty amines; quaternary ammonium salts such astetraalkylammonium, alkylamidoalkyltrialkyl-ammonium,trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridiniumchlorides or bromides; imidazoline derivatives; or amine oxides ofcationic nature.

[0232] The amounts of surfactants present in the composition accordingto the invention can range from 0.01% to 40% and preferably from 0.5% to30% relative to the total weight of the composition.

[0233] The compositions according to the invention may also compriseother agents for adjusting the rheology, such as cellulose-basedthickeners (hydroxyethylcellulose, hydroxypropylcellulose,carboxymethylcellulose, etc.), guar gum and its derivatives(hydroxypropylguar, etc.), gums of microbial origin (xanthan gum,scleroglucan gum, etc.), synthetic thickeners such as crosslinkedacrylic acid or acrylamidopropanesulfonic acid homopolymers andnonionic, anionic, cationic or amphoteric associative polymers, such asthe polymers sold under the names Pemulen TR1 or TR2 by the companyGoodrich, Salcare SC90 by the company Allied Colloids, Aculyn 22, 28,33, 44 or 46 by the company Rohm & Haas, and Elfacos T210 and T212 bythe company Akzo.

[0234] These additional thickeners may represent from 0.01% to 10% byweight relative to the total weight of the composition.

[0235] Another subject of the invention is a process for the oxidationdyeing of human keratin fibers, and in particular the hair, using a dyecomposition comprising, in a support that is suitable for dyeing saidfibers, at least one oxidation dye and an oxidizing composition asdefined above.

[0236] According to this process, at least one dye composition asdefined above is applied to the fibers, the color being developed atacidic, neutral or alkaline pH using an oxidizing composition accordingto the invention, which is applied simultaneously or sequentially, withor without intermediate rinsing.

[0237] According to one particularly preferred embodiment of the dyeingprocess according to the invention, the dye composition described aboveis mixed, at the time of use, with an oxidizing composition according tothe invention. The mixture obtained is then applied to the keratinfibers and is left to act for 3 to 50 minutes approximately andpreferably 5 to 30 minutes approximately, after which the fibers arerinsed, washed with shampoo, rinsed again and dried.

[0238] Another subject of the present invention is a process forpermanently reshaping human keratin fibers and in particular the hair,using the composition defined above as oxidizing composition.

[0239] According to this process, a reducing composition is applied tothe keratin fiber to be treated, the keratin fiber being placed undermechanical tension before, during or after said application, the fiberis optionally rinsed, the oxidizing composition of the present inventionis applied to the optionally rinsed fiber, and the fiber is thenoptionally rinsed again.

[0240] The first step of this process consists in applying a reducingcomposition to the hair. This application is performed lock by lock orto the whole head of hair.

[0241] The reducing composition comprises at least one reducing agent,which may be chosen in particular from thioglycolic acid, cysteine,cysteamine, glyceryl thioglycolate, thiolactic acid, or thiolactic acidor thioglycolic acid salts.

[0242] The usual step for placing the hair under tension in a shapecorresponding to the final shape desired for the hair (for examplecurls) may be performed by any means, especially any mechanical means,that is suitable and known per se for keeping the hair under tension,for instance rollers, curlers and the like.

[0243] The hair may also be shaped without the aid of external means,simply with the fingers.

[0244] Before performing the next optional rinsing step, it isconventionally appropriate to leave at rest for a few minutes, generallybetween 5 minutes and one hour and preferably between 10 and 30 minutes,the head of hair onto which the reducing composition has been applied,so as to allow the reducing agent sufficient time to act correctly onthe hair. This waiting phase preferably takes place at a temperatureranging from 35° C. to 45° C., preferably while also protecting the hairwith a hood.

[0245] In the second optional step of the process (step (ii)), the hairimpregnated with the reducing composition is then thoroughly rinsed withan aqueous composition.

[0246] Next, in a third step (step (iii)), the oxidizing compositionaccording to the present invention is applied to the hair thus rinsed,with the aim of fixing the new shape given to the hair.

[0247] As in the case of application of the reducing composition, thehead of hair onto which the oxidizing composition has been applied isthen, conventionally, left in a standing or waiting phase that lasts afew minutes, generally between 3 and 30 minutes and preferably between 5and 15 minutes.

[0248] The vehicle for the reducing and oxidizing compositions usedaccording to the invention is preferably an aqueous medium consisting ofwater and may advantageously contain cosmetically acceptable organicsolvents including, more particularly, alcohols such as ethyl alcohol,isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or polyols orpolyol ethers, for instance ethylene glycol monomethyl, monoethyl ormonobutyl ether, propylene glycol or its ethers, for instance propyleneglycol monomethyl ether, butylene glycol, dipropylene glycol, and alsodiethylene glycol alkyl ethers, for instance diethylene glycol monoethylether or monobutyl ether. The solvents may then be present inconcentrations of between about 0.5% and 20% and preferably betweenabout 2% and 10% by weight relative to the total weight of thecomposition.

[0249] If the hair was kept under tension by external means, these means(rollers, curlers and the like) may be removed from the hair before orafter the fixing step.

[0250] Finally, in the last step of the process according to theinvention (step (iv)), which is also an optional step, the hairimpregnated with the oxidizing composition is rinsed thoroughly,generally with water.

[0251] A head of hair that is soft and easy to disentangle is finallyobtained. The hair is wavy.

[0252] The oxidizing composition according to the invention may also beused in a process for bleaching human keratin fibers, and in particularthe hair.

[0253] The bleaching process according to the invention comprises a stepof applying an oxidizing composition according to the invention to thekeratin fibers, this composition preferably comprising aqueous hydrogenperoxide solution in alkaline medium after extemporaneous, mixing.Conventionally, a second step of the bleaching process according to theinvention is a step of rinsing the keratin fibers.

[0254] The examples that follow illustrate the invention without beinglimiting in nature.

PREPARATION EXAMPLES Preparation of ethoxylated (meth)acrylic esters

[0255] These may especially be obtained by the action ofglycidyl(meth)acrylate or (meth)acrylic acid or an alkyl(meth)acrylateor a (meth)acryloyl halide on an ethoxylated fatty alcohol. Nonlimitingexamples that may be mentioned include the following preparations:

[0256] a) starting with glycidyl methacrylate and Genapol T-250;

[0257] b) starting with (meth)acrylic acid and Genapol UD-070;

[0258] c) starting with methyl(meth)acrylate and Genapol LA-090;

[0259] d) starting with (meth)acryloyl chloride and Genapol UD-070.

[0260] a) 500 g of Genapol T-250 and 75 g of glycidyl methacrylate areplaced in a one-liter three-necked reactor equipped with a stirrer, athermometer and a reflux condenser. The reaction mixture is heated at atemperature of 100° C. for 2 hours and the excess glycidyl methacrylateis removed by distillation under reduced pressure. The monomer obtainedmay be used for the polymerization without further purification.

[0261] b) 500 g of Genapol UD-070, 100 g of (meth)acrylic acid andp-toluenesulfonic acid as catalyst are placed in a one-literthree-necked reactor equipped with a stirrer, a thermometer and a refluxcondenser. The reaction mixture is refluxed for 2 hours and the excessacid and the water formed during the reaction are separated out bydistillation under reduced pressure. The monomer obtained may be usedfor the polymerization without further purification.

[0262] c) 500 g of Genapol LA-090, 100 g of methyl(meth)acrylate and 20g of titanium tetraisopropoxide are placed in a one-liter three-neckedreactor equipped with a stirrer, a thermometer and a reflux condenser.The reaction mixture is refluxed for 2 hours and, after separation bydistilling off the alcohol formed, the remaining ester is distilledunder reduced pressure. The monomer obtained may be used for thepolymerization without further purification.

[0263] d) 500 g of Genapol UD-070, 110 g of (meth)acryloyl chloride and50 g of sodium carbonate are placed in a one-liter three-necked reactorequipped with a stirrer, a thermometer and a reflux condenser. Thereaction mixture is refluxed for 2 hours and the excess acid chloride isseparated out by distillation under reduced pressure. The monomerobtained may be used for the polymerization without furtherpurification.

Polymerization According to the Precipitation Method in tert-butanol

[0264] 500 ml of tert-butanol and the calculated amount of AMPS areplaced in a 2-liter reactor equipped with a reflux condenser, a gasinlet, a thermometer and a stirrer. The mixture is neutralized byintroducing NH₃, and the monomer prepared above is added to the reactionmixture. The reaction mixture is made inert by passing nitrogen or argonthrough, and, when the internal temperature has reached 60° C., theinitiator (AlBN) is introduced to initiate the polymerization.

[0265] After a few minutes, the polymer thus prepared precipitates. Themixture is maintained at reflux for 2 hours, and the polymer isseparated from the solvent by vacuum filtration and then dried underreduced pressure.

[0266] The following polymers were prepared in the manner describedabove: (starting with the following reagents in amounts expressed ingrams) Genapol T-250 methacrylate . . . 10 20 30 97 AMPS neutralizedwith NH₃ . . . 90 80 90 3 Methylenebisacrylamide 1.5 (crosslinkingagent) . . . Allyl methacrylate (crosslinking agent) . . . 1.7 TMPTA(crosslinking agent) . . . 1.8 1.8 Azobisisobutyronitrile (initiator) .. . 1 Dilauryl peroxide (initiator) . . . 1 1 1 tert-Butanol . . . 300300 300 300

EXAMPLE 1 Oxidation Dye Composition Dye Composition

[0267] The dark chestnut-brown shade from the commercial rangeExcellence Creme® from L'Oréal was used.

Oxidizing Composition

[0268] Acrylamido-2-methyl-2-propanesulfonic acid/ 1 gn-dodecylacrylamide copolymer (3.5%/96.5%) 100% neutralized with sodiumhydroxide . . . Hydrogen peroxide . . . qs . . . 20 volumes Tetrasodiumpyrophosphate (0.02 g) and sodium stannate (0.04 g) Sequestering agent:pentasodium pentaacetate . . . 0.06 g AM* Demineralized water . . .qs .. . 100 g

[0269] At the time of use, the dye composition was mixed with theoxidizing composition in a 1/1.5 weight ratio.

[0270] The mixture obtained was applied to locks of gray hair containing90% white hairs, at a rate of 10 g per 1 g of hair, and left to act for30 minutes.

[0271] The hair was then rinsed, washed with a standard shampoo and thendried.

[0272] A uniform dark chestnut-brown shade was obtained.

EXAMPLE 2 Permanent-Reshaping Composition

[0273] The reducing composition below (expressed in grams) was prepared:Thioglycolic acid . . . 9.2 Arginine . . . 15 Aqueous ammonia containing20% NH₃ . . . 9.3 Ammonium carbonate . . . 4.5Cocoylamidopropylbetaine/glyceryl monolaurate (25/5) as an 1.3 aqueous30% solution . . . Peptizer . . . 0.8 Isostearyl alcohol (Tego Alkanol66 sold by the company 12 Goldschmidt) . . . Sequestering agent . . .0.4 Fragrance . . . 0.4 Demineralized water . . . qs . . . 100

[0274] This reducing composition was applied to a lock of wet hairrolled up beforehand on a curler 9 mm in diameter.

[0275] After an action time of 10 minutes, the lock was rinsedthoroughly with water.

[0276] The oxidizing composition below was then applied.

Oxidizing Composition

[0277] Acrylamido-2-methyl-2-propanesulfonic acid/ 1 gn-dodecylacrylamide copolymer (3.5%/96.5%) 100% neutralized with sodiumhydroxide . . . Aqueous hydrogen peroxide solution . . . 8 volumesTetrasodium pyrophosphate (0.02 g) and sodium stannate (0.04 g)Sequestering agent: pentasodium pentaacetate . . . 0.06 g AM*Demineralized water . . . qs . . . 100 g

[0278] After an action time of 10 minutes, the lock was again rinsedthoroughly with water.

[0279] The hair was then unwound from the curler and dried.

[0280] The lock was wavy.

[0281] Similar results were obtained by replacing theacrylamido-2-methyl-2-propanesulfonic acid/n-dodecylacrylamide copolymerneutralized with sodium hydroxide, of the above Examples 1 and 2, with acopolymer crosslinked with methylenebisacrylamide consisting of 75% byweight of AMPS units neutralized with NH₃ and 25% by weight of units offormula (III) in which R₁═H, R₄═C₁₆-C₁₈ and x=25.

[0282] Similar results were obtained by replacing theacrylamido-2-methyl-2-propanesulfonic acid/n-dodecylacrylamide copolymerneutralized with sodium hydroxide, of the above Examples 1 and 2, with acopolymer crosslinked with allyl methacrylate consisting of 90% byweight of AMPS units neutralized with NH₃ and 10% by weight of GenapolT-250 methacrylate units [units of formula (III) in which R₁═CH₃,R₄═C₁₆-C₁₈ and x=25], or with a copolymer crosslinked with allylmethacrylate consisting of 80% by weight of AMPS units neutralized withNH₃ and 20% by weight of Genapol T-250 methacrylate units [units offormula (Ill) in which R₁═CH₃, R₄═C₁₆-C₁₈ and x=25].

1. A cosmetic and/or dermatological composition for treating keratinmaterials, characterized in that it comprises, in a support that issuitable for keratin materials: (a) at least one amphiphilic polymercomprising at least one ethylenically unsaturated monomer containing asulfonic group, in free form or partially or totally neutralized form,and also at least one hydrophobic portion, and (b) at least oneoxidizing agent.
 2. The composition as claimed in claim 1, characterizedin that the hydrophobic portion of the amphiphilic polymer contains from6 to 50 carbon atoms.
 3. The composition as claimed in claim 2,characterized in that the hydrophobic portion of the amphiphilic polymercontains from 6 to 22 carbon atoms.
 4. The composition as claimed inclaim 3, characterized in that the hydrophobic portion of theamphiphilic polymer contains from 6 to 18 carbon atoms.
 5. Thecomposition as claimed in claim 4, characterized in that the hydrophobicportion of the amphiphilic polymer contains from 12 to 18 carbon atoms.6. The composition as claimed in any one of claims 1 to 5, characterizedin that the amphiphilic polymers are partially or totally neutralizedwith a mineral or organic base.
 7. The composition as claimed in any oneof claims 1 to 6, characterized in that the amphiphilic polymers have anumber-average molecular weight ranging from 1000 to 20 000 000 g/mol.8. The composition as claimed in claim 7, characterized in that thenumber-average molecular weight ranges from 20 000 to 5 000 000 g/mol.9. The composition as claimed in claim 8, characterized in that thenumber-average molecular weight ranges from 100 000 to 1 500 000 g/mol.10. The composition as claimed in any one of the preceding claims,characterized in that an aqueous solution at 1% by weight of saidpolymers has, at a temperature of 25° C., a viscosity, measured using aBrookfield viscometer with a No. 7 needle, ranging from 20 000 mPa.s to100 000 mPa.s.
 11. The composition as claimed in any one of thepreceding claims, characterized in that the amphiphilic polymers areprepared by free-radical precipitation polymerization in tert-butanol.12. The composition as claimed in any one of the preceding claims,characterized in that the amphiphilic polymers are crosslinked ornoncrosslinked.
 13. The composition as claimed in claim 12,characterized in that the amphiphilic polymers are crosslinked.
 14. Thecomposition as claimed in claim 13, characterized in that thecrosslinking agent(s) is (are) chosen from polyolefinically unsaturatedcompounds.
 15. The composition as claimed in claim 14, characterized inthat the crosslinking agent(s) is (are) chosen frommethylenebisacrylamide, allyl methacrylate and trimethylolpropanetriacrylate (TMPTA).
 16. The composition as claimed in any one of claims13 to 15, characterized in that the degree of crosslinking preferablyranges from 0.01 mol % to 10 mol % and more particularly from 0.2 mol %to 2 mol % relative to the polymer.
 17. The composition as claimed inany one of the preceding claims, characterized in that the ethylenicallyunsaturated monomer containing a sulfonic group is chosen fromvinylsulfonic acid, styrenesulfonic acid,(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids andN—(C₁-C₂₂)alkyl(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids, and alsopartially or totally neutralized forms thereof.
 18. The composition asclaimed in claim 17, characterized in that the ethylenically unsaturatedmonomer containing a sulfonic group is chosen fromacrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid,acrylamidopropane-sulfonic acid, 2-acrylamido-2-methylpropanesulfonicacid, methacrylamido-2-methylpropanesulfonic acid,2-acrylamido-n-butanesulfonic acid,2-acrylamido-2,4,4-trimethylpentanesulfonic acid,2-methacrylamidododecylsulfonic acid and2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially ortotally neutralized forms thereof.
 19. The composition as claimed ineither of claims 17 and 18, characterized in that the ethylenicallyunsaturated monomer containing a sulfonic group is2-acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially ortotally neutralized forms thereof.
 20. The composition as claimed inclaim 19, characterized in that the amphiphilic polymers are chosen fromrandom AMPS polymers modified by reaction with ann-mono(C₆-C₂₂)alkylamine or a di-n-(C₆-C₂₂)alkylamine.
 21. Thecomposition as claimed in either of claims 19 and 20, characterized inthat the amphiphilic AMPS polymers also contain at least oneethylenically unsaturated monomer not comprising a fatty chain.
 22. Thecomposition as claimed in claim 20, characterized in that theethylenically unsaturated monomer not comprising a fatty chain is chosenfrom (meth)acrylic acids and β-substituted alkyl derivatives thereof,and esters thereof obtained with monoalcohols or mono- or polyalkyleneglycols, or alternatively from (meth)acrylamides, vinylpyrrolidone,maleic anhydride, itaconic acid or maleic acid, or mixtures of thesecompounds.
 23. The composition as claimed in any one of claims 1 to 19,characterized in that the amphiphilic AMPS polymers are chosen fromamphiphilic copolymers of AMPS and of at least one ethylenicallyunsaturated hydrophobic monomer comprising at least one hydrophobicportion containing from 6 to 50 carbon atoms.
 24. The composition asclaimed in claim 23, characterized in that the hydrophobic portioncontains from 6 to 22 carbon atoms.
 25. The composition as claimed inclaim 24, characterized in that the hydrophobic portion contains from 6to 18 carbon atoms.
 26. The composition as claimed in claim 25,characterized in that the hydrophobic portion contains from 12 to 18carbon atoms.
 27. The composition as claimed in any one of claims 23 to26, characterized in that the ethylenically unsaturated hydrophobicmonomer is chosen from the acrylates or acrylamides of formula (I)below:

in which R₁ and R₃, which may be identical or different, denote ahydrogen atom or a linear or branched C₁-C₆ alkyl radical (preferablymethyl); Y denotes O or NH; R₂ denotes a hydrophobic hydrocarbon-basedradical containing at least from 6 to 50 carbon atoms, more preferablyfrom 6 to 22 carbon atoms, even more preferably from 6 to 18 carbonatoms and more particularly from 12 to 18 carbon atoms; x denotes anumber of moles of alkylene oxide and ranges from 0 to
 100. 28. Thecomposition as claimed in claim 27, characterized in that thehydrophobic radical R₂ is chosen from linear, branched or cyclic C₆-C₁₈alkyl radicals; C₆-C₁₈ alkylperfluoro radicals; the cholesteryl radicalor a cholesterol ester; aromatic polycyclic groups.
 29. The compositionas claimed in either of claims 27 and 28, characterized in that themonomer of formula (I) also comprises at least one alkylene oxide unit(x≧1).
 30. The composition as claimed in any one of claims 27 to 29,characterized in that the monomer of formula (I) also comprises at leastone polyoxyalkylenated chain.
 31. The composition as claimed in claim30, characterized in that the polyoxyalkylenated chain consists ofethylene oxide units and/or of propylene oxide units.
 32. Thecomposition as claimed in claim 31, characterized in that thepolyoxyalkylenated chain consists solely of ethylene oxide units. 33.The composition as claimed in any one of claims 27 to 32, characterizedin that the number of oxyalkylene units ranges from 3 to
 100. 34. Thecomposition as claimed in claim 33, characterized in that the number ofoxyalkylene units ranges from 3 to
 50. 35. The composition as claimed inclaim 34, characterized in that the number of oxyalkylene units rangesfrom 7 to
 25. 36. The composition as claimed in any one of claims 23 to28, characterized in that the amphiphilic AMPS polymer is chosen from:crosslinked or noncrosslinked, neutralized or nonneutralized copolymerscomprising from 15% to 60% by weight of AMPS units and from 40% to 85%by weight of (C₈-C₁₆)alkyl(meth)acrylamide units or of(C₈-C₁₆)alkyl(meth)acrylate units relative to the polymer; terpolymerscomprising from 10 mol % to 90 mol % of acrylamide units, from 0.1 mol %to 10 mol % of AMPS units and from 5 mol % to 80 mol % ofn-(C₆-C₁₈)alkylacrylamide units relative to the polymer.
 37. Thecomposition as claimed in any one of claims 23 to 28, characterized inthat the amphiphilic AMPS polymer is chosen from: noncrosslinked andcrosslinked copolymers of partially or totally neutralized AMPS and ofn-dodecyl methacrylate; noncrosslinked and crosslinked copolymers ofpartially or totally neutralized AMPS and of n-dodecylmethacrylamide.38. The composition as claimed in claims 23 to 35, characterized in thatthe amphiphilic AMPS polymer is chosen from copolymers consisting of2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II)below:

in which X⁺ is a proton, an alkali metal cation, an alkaline-earth metalcation or the ammonium ion, and of units of formula (III) below:

in which x denotes an integer ranging from 3 to 100, preferably from 5to 80 and more preferably from 7 to 25; R₁ has the same meaning as thatgiven above in formula (I) and R₄ denotes a linear or branched C₆-C₂₂and more preferably C₁₀-C₂₂ alkyl.
 39. The composition as claimed inclaim 38, characterized in that x=25, R₁ is methyl and R₄ is n-dodecyl.40. The composition as claimed in claim 27 or 38, characterized in thatthe molar percentage proportion of units of formula (I) or of units offormula (III) in the polymers ranges from 50.1% to 99.9%.
 41. Thecomposition as claimed in claim 27 or 38, characterized in that themolar percentage proportion of units of formula (I) or of units offormula (III) in the polymers ranges from 0.1% to 50%.
 42. Thecomposition as claimed in any one of the preceding claims, characterizedin that the amphiphilic polymers are present in concentrations rangingfrom 0.01% to 30% by weight, more preferably from 0.1% to 10% by weight,even more preferably from 0.1% to 5% by weight and even moreparticularly from 0.5% to 2% by weight relative to the total weight ofthe composition.
 43. The composition as claimed in any one of claims 1to 42, characterized in that the oxidizing agent is chosen from thegroup formed by hydrogen peroxide, urea peroxide, perborates andpersulfates, or mixtures thereof.
 44. The composition as claimed in anyone of claims 1 to 43, characterized in that the oxidizing agent ishydrogen peroxide.
 45. The composition as claimed in claim 44,characterized in that the hydrogen peroxide concentration ranges from0.5 to 40 volumes and preferably from 2 to 30 volumes.
 46. Thecomposition as claimed in claim 44, characterized in that the oxidizingagent is aqueous hydrogen peroxide solution.
 47. The composition asclaimed in claim 46, characterized in that the aqueous hydrogen peroxidesolution contains a stabilizer.
 48. The composition as claimed in claim47, characterized in that the stabilizer is chosen from alkali metal oralkaline-earth metal pyrophosphates, alkali metal or alkaline-earthmetal stannates, phenacetin or salts of acids and of oxyquinoline. 49.The composition as claimed in claim 48, characterized in that thestabilizer is a stannate or a stannate combined with a pyrophosphate.50. The composition as claimed in any one of claims 46 to 49,characterized in that the stabilizer concentration ranges from 0.0001%to 5% by weight and preferably from 0.01% to 2% by weight relative tothe total weight of the composition.
 51. The composition as claimed inany one of claims 44 to 50, characterized in that the ratio of theconcentrations of the hydrogen peroxide to the stabilizers ranges from0.05 to 1000, preferably from 0.1 to 500 and more particularly from 1 to200.
 52. The composition as claimed in any one of claims 44 to 51,characterized in that the ratio of the concentrations of the amphiphilicpolymer(s) defined as claimed in claims 1 to 42 to the stabilizersranges from 0.05 to 1000, preferably from 0.1 to 500 and moreparticularly from 1 to
 200. 53. The composition as claimed in any one ofthe preceding claims, characterized in that the ratio of theconcentrations of the amphiphilic polymer(s) defined as claimed inclaims 1 to 42 to the oxidizing agents ranges from 0.001 to 10,preferably from 0.01 to 5 and more particularly from 0.02 to
 1. 54. Thecomposition as claimed in any one of claims 43 to 52, characterized inthat the concentration of oxidizing agents ranges from 0.1% to 25% byweight relative to the total weight of the composition.
 55. Thecomposition as claimed in any one of claims 1 to 54, characterized inthat it is aqueous and in that the pH of the whole composition rangesfrom 1 to 13 and preferably from 2 to
 12. 56. The composition as claimedin any one of claims 1 to 55, characterized in that it is in the form ofa transparent gel with a viscosity ranging from 50 mPa.s to 10 Pa.s andmore preferably from 75 mPa.s to 0.5 Pa.s.
 57. A process for theoxidation dyeing of human keratin fibers, and in particular the hair,using a dye composition comprising, in a support that is suitable fordyeing keratin fibers, at least one oxidation dye and an oxidizingcomposition as defined in any one of claims 1 to
 56. 58. The dyeingprocess as claimed in claim 57, according to which the dye compositionis mixed, at the time of use, with the oxidizing composition; themixture obtained is then applied to the keratin fibers and is left toact for 3 to 50 minutes approximately and preferably 5 to 30 minutesapproximately, after which the fibers are rinsed, washed with shampoo,rinsed again and dried.
 59. The dyeing process as claimed in claim 57,according to which the dye composition and the oxidizing composition areapplied sequentially, with or without intermediate rinsing.
 60. Aprocess for treating human keratin fibers, and in particular the hair,to permanently reshape these fibers, in particular in the form ofpermanent-waved hair, this process comprising the following steps: (i) areducing composition is applied to the keratin material to be treated,the keratin fiber being placed under mechanical tension before, duringor after said application, (ii) the keratin fiber is optionally rinsed,(iii) an oxidizing composition as defined in one of claims 1 to 56 isapplied to the optionally rinsed keratin fiber, (iv) the keratin fiberis optionally rinsed again.
 61. A process for bleaching human keratinfibers, and in particular the hair, comprising the following steps: i)an oxidizing composition as claimed in any one of claims 1 to 56 isapplied to the keratin fiber, ii) the keratin fiber thus treated isrinsed.
 62. The use, as a thickener and/or gelling agent in a cosmeticand/or dermatological composition comprising at least one oxidizingagent, of an amphiphilic polymer as defined in any one of claims 1 to42. The invention concerns a cosmetic composition for treatingkeratinous materials comprising in a carrier suitable for keratinousmaterials: (a) at least an amphiphilic polymer comprising at least anethylenically unsaturated monomer with sulphonic group, in free form orpartly or completely neutralised and further at least a hydrophobicpart; (b) at least an oxidising agent.